PSAL colloque ANR MatetPro ECL Nantes Octobre 2013 pour

DEVELOPPEMENT D’UN PROCEDE
DE SELECTION DE NOUVEAUX
ADDITIFS DE LUBRIFICATION
APPLICATION AUX POLYSULFURES
PSAL -­‐ N° PROJET ANR (05-­‐RNMP-­‐014-­‐01) DEVELOPPEMENT D’UN PROCEDE DE SELECTION DE
NOUVEAUX ADDITIFS DE LUBRIFICATION.
APPLICATION AUX POLYSULFURES
Programme: ANR Mat&Pro édi3on 2005 Acronyme : PSAL Durée du projet : 36 mois (01/01/2005 au 31/12/2007) Financement : 693329 € 3 Partenaires : LTDS-­‐Ecole Centrale de Lyon, Dr. Maria Isabel De Barros Bouchet LSA-­‐Université Claude Bernard Lyon 1 Pr. Didier Léonard Groupement de Recherche de Lacq-­‐ARKEMA Dr. Patrick Charles MOTS CLES : Simula[on Expérimentale, Lubrifica[on Limite, Tribochimie, Addi[fs de Lubrifica[on, Mécanismes Réac[onnels. PSAL -­‐ N° PROJET ANR (05-­‐RNMP-­‐014-­‐01) Boundary Lubrication
a real challenge for today's society
Transportation
Metalworking
In most industrialized countries, the annual cost of fric[on and wear energy loss is es[mated between 5 and 7% of Gross Domes[c Product (GDP) Tribology for Energy Efficiency and Environmental Protection…
Requirements for Next Generation Oils
ü 　Becer energy economy (fuel consump[on for engines) ü 　Longer life (mechanical components and less oil drainings) ü 　Lower emissions ・　Low phosphorous　・　Low sulfur ・　Low ash (diesel) ⇒ Compa[bility with exhaust treatment devices CO2 emissions for new vehicules in 1998 (ACEA)
Role of lubricant in Tribology
Lubricant
=
Base oil
+
Package of performance additives
Dispersants
41%#
26%#
Detergents
Viscosity
modifiers 20%#
4%#
Oxidation
inhibitors
8%#
1%#
Surface Additives
(AW, FM, EP)
Tribofilm
Needs for simplification of tribological systems
Nascent
metallic surface
Ø  Control of the contact surfaces: fric[on made on oxidized or metallic surfaces Additive 1
P in
(S t e e l A I S I 5 2 1 0 0 )
3 .5 N
(P 0 =
Oxidized
surface
Iden[fica[on of keys of tribochemical mechanisms Ø  Ability to simulate the ac3on of a unique addi3ve without any rheological effect of the base Iden[fica[on of addi[ve ac[on Additive 1
(P
= 3. 5N Pin
(Steel AISI 52100)
0
Metallic
surface
Additive 2
Oxidized
surface
Ø  Ability to study interac3ons between different addi3ves or base oil/addi3ves Iden[fica[on of compe[[ve effects between addi[ves Ø  Prevent the contamina3on or denatura3on of the tribological surfaces by air exposure or cleaning solvents Accurate iden[fica[on of tribofilm nature Gas Phase Tribology for in situ Surface Analysis
In situ
Ex situ
Multi ex situ surface analysis approach
with 1nm Depth Resolution
X-Ray Photoelectron Spectroscopy (XPS)
Auger Electron Spectroscopy (AES)
X-ray Absorption Near Edge Structure (XANES)
Static Secondary Ions Mass Spectroscopy (SSIMS)
XPS
in situ surface analysis with
1nm Depth Resolution
X-Ray Photoelectron Spectroscopy (XPS)
Auger Electron Spectroscopy (AES)
XANES
SSIMS
AES
Probe
Electrons
Photons
Electrons Electrons
Signal
Depth resolution 0.5-10nm 0.5-5nm
Photons
Ions
Electrons
Ions
0.5-5nm
0.1-1nm
1x10-4
Information Elemental
Chemical
Spatial resolution 0.1-30µm
1x10-4
1x10-7
Elemental Elemental
Molecular Molecular
500nm
120nm
Detection limit
Material
All
1x10-3
Elemental
50 nm
Conductive
All
All
Gas Phase Tribometer
XPS/AES Thermo 250i • 
• 
• 
• 
• 
• 
XPS/AES
XPS/AES
Analysis
chamber
Brushles
s motor
Transfer
mechanism
Preparation chamber
Brushless
motor
Fast entry
Fast entry
loadloadmechanism
mechanism
Fast entry
loadmechanism
ECT
ECT
Electron gun FEG1000 (spot size 0,1 µm) Dual X-­‐ray source (Mg Kα / Al Kα) Focused (250 µm) and monochroma[c Al X-­‐ray source Ion gun VG X05 Small area analysis (80 µm) Surface imaging: Op[cal SEM AES XPS •  Annealing up to 1000°C •  Film deposi[on facili[es: Thermal evapora[on Magnetron spucering Transfer
Transfer
mechanism
mechanis
m
Turbomolecula
Turbomolecul
r pump
ar pump
ECT
• 
• 
• 
• 
• 
• 
• 
Pin-­‐on-­‐flat contact Linear reciproca3ng mo3on Speed: 0.005 to 5 mm.s-­‐1 Length of track :0.05 to 5 mm Load: 0.1 to 10 N Temperature: -­‐100 to 600°C Gas pressure: 10-­‐9 to 2000 hPa Experimental simulation of boundary lubrication reactions
Environmental Controlled Analytical Tribometer (ECAT)
Advantages of Gas Phase Lubrica3on • 
• 
• 
• 
• 
Simplifica[on of tribological system, study of one or more addi[ve molecules; Control of the contact surfaces: oxidized, etched or nascent metallic surfaces; Iden[fica[on of compe[[ve effects and interac[ons between the addi[ve molecules; In situ (XPS/AES) surface analyses; Weak adsorp[on of molecules aker the end of fric[on test avoiding then the masking of tribofilm. Limita3ons of Gas Phase Lubrica3on • 
• 
• 
• 
Only light molecular weigth molecules can be easily introduced in gas phase; Possible desorp[on of light molecules at high temperatures, compromise between adsorp[on/desorp[on; Kine[c of forma[on of tribofilms in GPL is mostly lower than in LPL. Limita[on of the varia[on range of tribological parameters, AW condi3ons (P= 520 MPa) are OK but EP condi[ons are difficult to acheive (P≈1 GPa). PSAL -­‐ N° PROJET ANR (05-­‐RNMP-­‐014-­‐01) New strategies in Boundary Lubrication
New strategies in Boundary Lubrication
ü  Reduction of S and P contents in oils using Low SAPS
additives technology for ferrous materials
(SAPS : Sulfated Ash, Phosphorus and Sulphur);
2000
Organo-sulfurs (FM, EP), …
ü  Use of Nanolubricants (colloids, CNT,
Fullerenes, carbon onions……) as additives
for ferrous materials;　ü  Use of carbon coatings (DLC et NCD) and new
additives technology containing ashless (CHO) additives
(No SAPS additives technology);
2001
2009
Lubrication of
non-ferrous materials
Contribution of Gas Phase Tribology
in Organo-Sulfurs Tribochemistry
Thèse de doctorat de Mr. J. Tannous (2007)
Partenaire industriel ARKEMA
PSAL -­‐ N° PROJET ANR (05-­‐RNMP-­‐014-­‐01) Tribochemistry of organo-sulfurs molecules
Organo-sulfurs
Lubricant Additive
Polysulfides
(EP +FM)
TPS
Model Molecule
for GPL
TPS 44
(Pvap. sat.≈ 3 hPa at Troom) (supplied by ARKEMA group) Alkanethiols
C6H14S (Pvap. sat.> 3 hPa at Troom) (supplied by ARKEMA group) PSAL -­‐ N° PROJET ANR (05-­‐RNMP-­‐014-­‐01) Comparison between polysulfides (TPS) and alkanethiols
Friction and wear
Sliding speed : 0.5 mm/s AISI 52100 steel specimens Pcontact = 520 MPa T : 30°C and 80°C Fric[on coefficient TPS (3hPa) 165 µm 500µm
Thiol (3hPa) 500µm
Cycles number J. TANNOUS, M.I. De BARROS BOUCHET et al., Tribology-­‐Materials, Surfaces and Interface, vol. 1, N°2 (2007) p.98-­‐104. ü  Polysulfides are effec[ve in reducing fric[on and wear but less than alkanethiols. ü  Forma[on of a tribofilm in the presence of polysulfides? Comparison between polysulfides (TPS) and alkanethiols
Tribofilm chemical nature
In situ XPS S2p sectra (S-­‐Fe) Disulfide FeS2 Tribofilm TPS (S−Fe) Sulfide FeS S−O Outside track Tribofilm Thiol Binding energy (eV) Iron sulfide (FeS) Iron disulfide (FeS2) Binding energy (eV) ü  Alkanethiol-­‐derived tribofilm is mainly composed of iron sulfide FeS. ü  TPS-­‐derived tribofilm is mainly composed of iron disulfide FeS2 , with some FeS. ü  These results were confirmed by ToF-­‐SIMS analyses. Mécanisme de formation des sulfures de fer
R S Fe S S R R S R Fe Etape 3
Décomposition due
composés soufrés
activée par le
cisaillement
fer (acier) Etape 1
Elimination de la couche
Etape 2
d’oxyde lors du
Adsorption des composés
frottement
soufrés sur un site actif
de fer métallique
oxyde de fer fer (acier) R R S S S R Fe Fe fer (acier) Etape 4
Formation de FeS et/ou FeS2
adsorption/décomposition
des groupes carbonés
S Fe R fer (acier) S R S Fe S Fe Etape 5
Tribofilm contenant du
FeS et/ou FeS2
+ produits de réaction
adsorbés en surfaces
R R fer (acier) S S Fe S R Summarizing
Ø  Gas Phase Tribology can simulate the Liquid Phase Tribology under
Boundary Lubrication regime. It is a powerful tool to understand the
tribochemistry of lubricant additives.
Ø  The ECAT device was developed to realize the experimental simulation of
tribochemical reactions under BL regime.
Ø  Optimization of lubrication additives packages in order to increase
performances ?
- Interactions between different kinds of lubricant additives, AW, FM, EP,…
- Effect of tribological conditions on the tribochemical mechanisms?
their
Bilan du Projet
publications et communications
Ar3cles acceptés dans revues à comité de lecture 1-­‐ Contribu[on of gas phase lubrica[on in understanding the tribochemistry of organosulphur compounds ; J. TANNOUS, M.I. De BARROS BOUCHET, Th. LE MOGNE, P. CHARLES, J.M. MARTIN , Tribology-­‐Materials, Surfaces and Interface, vol. 1, N°2 (2007) p.98-­‐104, 2-­‐ Role of nascent metallic surfaces on the tribochemistry of phosphite lubricant addi[ves, D. Philippon, M.I. De Barros Bouchet, T. Le-­‐Mogne, O. Lerasle and J.M. Mar[n, Tribology Interna[onal, (2009). 3-­‐ Experimental simula[on of tribochemical reac[ons between borates esters and steel surface, D. Philippon, M.I. De Barros Bouchet, T. Le-­‐Mogne, O. Lerasle and J.M. Mar[n, Tribology Lecers 41 (1) (2011):73-­‐82. 4-­‐ A mul[-­‐technique approach to the characteriza[on of iron phosphide tribofilm; D. Philippon, M.I. De Barros-­‐Bouchet, Th. Le-­‐Mogne, B. Vacher, O. Lerasle, J-­‐M. Mar[n, Thin Solid Films 524 (1) (2012) 191–196. + 1 soumise et 1 en cours de rédac3on… Communica3ons Interna3onales 1-­‐ Experimental Simula[on of Organosulphurs Tribochemical Reac[ons, J. TANNOUS, M.I. DE BARROS BOUCHET, P. CHARLES, Th. LE-­‐MOGNE, J-­‐M MARTIN ; Fron[ers in Boundary Lubrica[on Films. Conference Interna[onale, April 9-­‐14, 2006, Lyon, France. (Poster). 2-­‐ Tribochemistry of Organo-­‐Sulphurs Compounds, J. TANNOUS, M.I. DE BARROS BOUCHET, P. CHARLES, Th. LE-­‐MOGNE, J-­‐M MARTIN, 33rd Leeds-­‐Lyon on Tribology, 12th-­‐15th September 2006, Trinity and all saints college, the University of Leeds, UK. (Présenta[on orale). 3-­‐ Experimental Modelisa[on of Organosulphurs Tribochemistry by Gas Phase Lubrica[on, J. TANNOUS, M.I. DE BARROS BOUCHET, P. CHARLES, Th. LE-­‐MOGNE, J-­‐M MARTIN, STLE/ASME Interna[onal Joint Tribology Conference, October 22-­‐24, 2007, San Diego, California, USA. (Présenta[on orale). 4-­‐ Experimental Simula[on of Organo-­‐Sulphur Addi[ves Tribochemistry under Boundary Lubrica[on Regime by Gas Phase Lubrica[on, M.I. DE BARROS BOUCHET, J. TANNOUS, P. CHARLES, Th. LE-­‐MOGNE, J-­‐M MARTIN, Advances in Boundary Lubrica[on and Boundary Surface Films Conference ECI, March, 2009 Seville, Spain. (Présenta[on orale). 5-­‐ Understanding of the Tribochemistry of Organo-­‐Sulfur Compounds, M. I. DE BARROS BOUCHET, J. TANNOUS, T. LE MOGNE, P. CHARLES and J. M. MARTIN, 4th Wolrd Tribology Congress, 6-­‐11 Septembre 2009, Kyoto, Japon. (Présenta[on orale). 6-­‐ ToF-­‐SIMS Study of Tribochemical Proper[es of Sulfur-­‐Based Addi[ves for the Lubrica[on of Steels in Boundary Lubrica[on Condi[ons, D. LEONARD, M. GOUELLO, J. TANNOUS, S. GOUT, F. BESSUEILLE, M.I DE BARROS BOUCHET, Th. LE MOGNE, J-­‐M MARTIN, P. CHARLES, 17th Interna[onal Conference on Secondary Ion Mass Spectrometry, Toronto 13-­‐18 Septembre 2009. (Présenta[on orale). +… Bilan du Projet
Eléments de valorisation
Conséquences du projet (lancement de produit ou service, nouveau projet, contrat,…) : -­‐ 
Nouveau projet ANR MatetPro 2010 « ECOLUB » avec 5 partenaires. -­‐ 
Mise en place d’un partenariat scien[fique entre 2 laboratoires LTDS/LSA autour d’ou[ls d’analyses.